EP0077066A1 - Method of preparing azo dyestuffs by diazotation and coupling - Google Patents

Method of preparing azo dyestuffs by diazotation and coupling Download PDF

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Publication number
EP0077066A1
EP0077066A1 EP82109414A EP82109414A EP0077066A1 EP 0077066 A1 EP0077066 A1 EP 0077066A1 EP 82109414 A EP82109414 A EP 82109414A EP 82109414 A EP82109414 A EP 82109414A EP 0077066 A1 EP0077066 A1 EP 0077066A1
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Prior art keywords
formula
carbazole
acetic acid
amine
weight
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German (de)
French (fr)
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EP0077066B1 (en
Inventor
Ulrich Dr. Bühler
Wolfgang Dr. Bodenstedt
Heinz Hänel
Eberhard Dr. Hebestreit
Horst Dr. Tappe
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Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
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Cassella AG
Cassella Farbwerke Mainkur AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B41/00—Special methods of performing the coupling reaction
    • C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
    • C09B41/002—Special methods of performing the coupling reaction characterised by the coupling medium containing a solvent

Definitions

  • the present invention relates to a process for the preparation of azo dyes of the formula I. in the hal bromine or chlorine and R optionally substituted by hydroxy, cyano, alkoxy with 1 to 4 carbon atoms or alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, alkoxyalkoxycarbonyl with 1 to 4 carbon atoms in each of the two alkoxy radicals with 1 to 4 carbon atoms or hydrogen, by diazotization of an amine of the formula II and coupling the diazotized amine to a carbazole of the formula III and isolating the dye after coupling is complete.
  • Azo dyes are usually prepared by diazotization and coupling in an aqueous medium.
  • Dyes of the formula I can only be prepared by this process in poor yields and purities, since the solubility ratios, in particular of the coupling component, are unfavorable.
  • other diazotization and coupling processes for the preparation of the dyes of the formula I also only give them in moderate yields. With the Low yields are usually associated with the occurrence of impurities, which means that the dyes thus obtained have to be recrystallized before use.
  • Some processes use various organic solvents to dissolve the coupling component and wash the dye, which are extremely difficult to regenerate.
  • the diazo component is diazotized in glacial acetic acid and coupled to carbazole, which is dissolved in dimethylformamide, and the isolated dye is washed with methanol and water. In this process, a water-containing mixture of three organic solvents must therefore be regenerated.
  • carbazole is suspended in butanol for coupling.
  • the dye yield here is approximately 82%.
  • up to 18% of 3-chloronitrobenzene is formed, which either cannot be separated quantitatively from the dye during the work-up or is enriched in butanol and leads to problems during the work-up.
  • the process of the Swiss patent specification 367 254 relates to a process for the preparation of water-poorly soluble monoazo dyes, in which, according to example 1, the coupling component is dissolved in glacial acetic acid. Applying this process to the preparation of the dye of the formula I, in which Hal is chlorine and R is ethyl, a yield of 80% is obtained.
  • This dye, dyed on polyester, is about 50% weaker in color than that produced by the process according to the invention.
  • Example 1 of US Pat. No. 3,787,178 the diazo component is added to a mixture of nitrosylsulfuric acid, glacial acetic acid and propionic acid. Then a solution of butyl carbazole in glacial acetic acid is added. If this process is applied to the preparation of the dye of the formula I in which Hal is chlorine and R is hydrogen, a blackish powder is obtained which contains only about 46% by weight of the desired dye.
  • the process according to the invention for the preparation of the dyes of the formula I is characterized in that the amine of the formula II is diazotized in 70 to 100 percent by weight acetic acid at 10 to 35 ° C. with nitrosylsulfuric acid, the acetic acid content of the diazo solution by adding water to 60 to 85% by weight. % reduced and a carbazole of the formula III in solid form or in the form of a suspension in 60 to 100 percent by weight acetic acid is introduced at 15 to 45 ° C.
  • Suitable amines of the formula II are 2-chloro-4-nitraniline and 2-bromo-4-nitraniline.
  • the alkyl radical representing R and the alkoxy, alkoxycarbonyl or alkoxyalkoxycarbonyl radicals which are suitable as substituents for R can be straight-chain or branched.
  • Examples of carbazoles of the formula III are: carbazole, furthermore carbazoles which are substituted on the nitrogen by the following radicals: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, 2-hydroxyethyl , 4-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 2-i-propoxyethyl, 2-n-butoxyethyl, 2-i-butoxy ethyl, 3-methoxybutyl, 4-methoxybutyl, 2-cyanoethyl, 2-methoxycarbonylethyl or 2-ethoxycarbonylethyl.
  • the amine of formula II is in 70 to 100 percent by weight, preferably in 85 to 95 percent by weight, very particularly preferably in 88 to 92 percent by weight acetic acid at temperatures of 10 to 35 ° C., preferably 10 to 30 ° C., with nitrosylsulfuric acid, advantageously with stirring , diazotized. It is expedient if the amine of the formula II is present in dissolved or finely divided form in the acetic acid before or during the diazotization.
  • the desired fine distribution is achieved, for example, in that the amine of the formula II is dissolved as completely as possible in the acetic acid before the addition of the nitrosylsulfuric acid with stirring at from 15 to 50 ° C., preferably 20 to 40 ° C., and then the solution is dissolved the diazotization temperature is cooled, as a result of which the precipitating amine precipitates out in a fine distribution.
  • the diazotization of the amine of the formula II with nitrosylsulfuric acid should take place rapidly, ie within 5 to 45, preferably within 5 to 20 minutes, since otherwise the triazene of the formula IV would form, which is very sparingly soluble in the acetic acid used and would therefore fail. This could lead to local overheating and thus to the decomposition of the diazonium compound still present, to the stirrer stoppage and lead to termination of the desired reaction.
  • the rapid addition of nitrosylsulfuric acid quickly makes the environment so acidic that only a little free amine of the formula II is present and the formation of triazene is largely prevented.
  • Triazene of the formula IV formed to a small extent is split back at the temperatures used in the process according to the invention, and the amine of the formula II which is released in the process is quantitatively further diazotized. Since the addition of the nitrosylsulfuric acid is exothermic and, on the other hand, the diazo solution must not be heated too much, the addition time for the nitrosylsulfuric acid depends primarily on the intensity with which it is possible to cool during the diazotization.
  • the diazotization is expediently started just above the temperature at which the solution or suspension of the amine of the formula II becomes solid, it then being possible to keep the temperature below 25 to 35 ° C. by ice cooling.
  • stirring is continued for some time to complete the diazotization and then the acetic acid content of the diazo solution is reduced to 60 to 85% by weight, preferably to 68 to 73% by weight, by adding water.
  • the addition of water should not drop the acetic acid content of the diazo solution below 60% by weight, since otherwise the coupling component will no longer dissolve sufficiently or the stability of the diazonium compound will decrease.
  • nitrite-interfering agents such as urea or amidosulfonic acid.
  • agents can be added to the diazo solution before or after dilution with water.
  • the coupling is carried out at temperatures of 15 to 45 ° C, preferably 20 to 35 ° C, by the carbazole of formula III slowly, for example in the course of 1/2 to 2 hours, is expediently introduced into the diazo solution with stirring.
  • the carbazole of the formula III should advantageously be in a fine distribution. When a carbazole of the formula III is introduced in solid form, the fine distribution may have been brought about, for example, by grinding the carbazole beforehand.
  • the carbazole of the formula III When the carbazole of the formula III is introduced in the form of a suspension in acetic acid, the carbazole of the formula III is expediently first completely dissolved in 50 to 50 times the amount of 60 to 100 percent by weight acetic acid by heating and then to a temperature which does not exceed the coupling temperature is cooled, whereby the precipitated carbazole of the formula III precipitates in a fine distribution.
  • the acetic acid content of the coupling batch must not be pressed below 60% by weight or raised above 85% by weight due to the acetic acid of the suspension.
  • the addition time for the carbazole of the formula III depends on the batch size and is expediently extended to 1 to 2 hours in batches on a kg scale.
  • the coupling temperature must not fall below 15 ° C, otherwise the carbazole derivative entered will dissolve too poorly and coupling times will be too long, or the dye purity and yield will decrease, since the dye which precipitates includes the coupling component or the diazonium compound will decompose if the reaction time is too long. It is expedient to couple at 20 to 3 ° C. and to complete the reaction at temperatures up to 40 ° C.
  • Dye formed during the coupling precipitates, so that almost the entire amount of acetic acid used is available as a solvent for the diazonium compound and the coupling component.
  • the process according to the invention provides the dyes of the formula I in yields of up to 99% and more, in excellent units.
  • the low purities result in higher color strengths in the coloristic application and mostly also better values for the fastness to dry heat pleating and dry heat compared to dyes which have been produced by other processes.
  • the acetic acid solution obtained in the process according to the invention can be regenerated again.
  • Dye yield 345.5 g dry, purity 99.6%, corresponding to 98.6% yield of theory; Melting point 218 to 224 ° C.
  • the dyes listed in the following table can be prepared by the process according to the invention:

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Abstract

Bei dem Verfahren zur Herstellung von Azofarbstoffen der Formel I <IMAGE> in der Hal Brom oder Chlor und R gegebenenfalls substituiertes Alkyl mit 1 bis 4 C-Atomen oder Wasserstoff bedeutet, wird ein Amin der Formel II <IMAGE> in 70 bis 100 gewichtsprozentiger Essigsäure bei 10 bis 35°C mit Nitrosylschwefelsäure diazotiert, der Essigsäuregehalt der Diazolösung durch Zugabe von Wasser auf 60 bis 85 Gew.-% reduziert und bei 15 bis 45°C ein Carbazol der Formel III <IMAGE> in 60 bis 100 gewichtsprozentiger Essigsäure eingetragen.In the process for the preparation of azo dyes of the formula I <IMAGE> in which Hal is bromine or chlorine and R is optionally substituted alkyl having 1 to 4 carbon atoms or hydrogen, an amine of the formula II is <IMAGE> in 70 to 100 percent by weight acetic acid diazotized at 10 to 35 ° C with nitrosylsulfuric acid, the acetic acid content of the diazo solution reduced to 60 to 85% by weight by adding water and a carbazole of the formula III <IMAGE> in 60 to 100% by weight acetic acid introduced at 15 to 45 ° C.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Azofarbstoffen der Formel I

Figure imgb0001
in der Hal Brom oder Chlor und R gegebenenfalls durch Hydroxy, Cyan, Alkoxy mit 1 bis 4 C-Atomen oder Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkoxyrest, Alkoxyalkoxycarbonyl mit jeweils 1 bis 4 C-Atomen in den beiden Alkoxyresten, substituiertes Alkyl mit 1 bis 4 C-Atomen oder Wasserstoff bedeutet, durch Diazotierung eines Amins der Formel II
Figure imgb0002
und Kupplung des diazotierten Amins auf ein Carbazol der Formel III
Figure imgb0003
und Isolieren des Farbstoffs nach beendeter Kupplung.The present invention relates to a process for the preparation of azo dyes of the formula I.
Figure imgb0001
 in the hal bromine or chlorine and R optionally substituted by hydroxy, cyano, alkoxy with 1 to 4 carbon atoms or alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, alkoxyalkoxycarbonyl with 1 to 4 carbon atoms in each of the two alkoxy radicals with 1 to 4 carbon atoms or hydrogen, by diazotization of an amine of the formula II
Figure imgb0002
 and coupling the diazotized amine to a carbazole of the formula III
Figure imgb0003
 and isolating the dye after coupling is complete.

Azofarbstoffe werden üblicherweise durch Diazotierung und Kupplung im wäßrigen Medium hergestellt. Nach diesem Verfahren können Farbstoffe der Formel I nur in schlechten Ausbeuten und Reinheiten hergestellt werden, da die Löslichkeitsverhältnisse insbesondere der Kupplungskomponente ungünstig liegen. Aber auch andere Diazotierungs- und Kupplungsverfahren zur Herstellung der Farbstoffe der Formel I liefern sie nur in mäßigen Ausbeuten. Mit den geringen Ausbeuten ist meist das Auftreten von Verunreinigungen verbunden, was dazu führt, daß die so erhaltenen Farbstoffe vor der Verwendung umkristallisiert werden müssen. Bei-einigen Verfahren werden zum Lösen der Kupplungskomponente und zum Waschen des Farbstoffs verschiedeneorganische Lösungsmittel eingesetzt, deren Regeneration äußerst schwierig ist.Azo dyes are usually prepared by diazotization and coupling in an aqueous medium. Dyes of the formula I can only be prepared by this process in poor yields and purities, since the solubility ratios, in particular of the coupling component, are unfavorable. However, other diazotization and coupling processes for the preparation of the dyes of the formula I also only give them in moderate yields. With the Low yields are usually associated with the occurrence of impurities, which means that the dyes thus obtained have to be recrystallized before use. Some processes use various organic solvents to dissolve the coupling component and wash the dye, which are extremely difficult to regenerate.

So wird gemäß der DE-OS 22 12 755 die Diazokomponente in Eisessig diazotiert und auf Carbazol, das in Dimethylformamid gelöst ist, gekuppelt und der isolierte Farbstoff mit Methanol und Wasser gewaschen. Bei diesem Verfahren muß somit ein wasserhaltiges Gemisch von drei organischen Lösungsmitteln regeneriert werden.Thus, according to DE-OS 22 12 755, the diazo component is diazotized in glacial acetic acid and coupled to carbazole, which is dissolved in dimethylformamide, and the isolated dye is washed with methanol and water. In this process, a water-containing mixture of three organic solvents must therefore be regenerated.

Nach den Lehren der DE-OS 26 03 836 wird Carbazol zur Kupplung in Butanol suspendiert. Die Farbstoffausbeute beträgt hier ca. 82 %. Daneben entsteht jedoch 3-Chlornitrobenzol bis zu 18 %, das sich bei der Aufarbeitung entweder vom Farbstoff nicht quantitativ abtrennen läßt oder sich in Butanol anreichert und zu Problemen bei der Aufarbeitung führt.According to the teachings of DE-OS 26 03 836, carbazole is suspended in butanol for coupling. The dye yield here is approximately 82%. In addition, however, up to 18% of 3-chloronitrobenzene is formed, which either cannot be separated quantitatively from the dye during the work-up or is enriched in butanol and leads to problems during the work-up.

Weiter werden in Collect. Czechoslov. Chem. Comm. 25, 1324 (1960) und 29, 2264 (1964) Syntheseverfahren beschrieben, bei denen Carbazol in Dioxan bzw. in Ethanol gekuppelt wird. Die Ausbeuten betragen im einen Fall 55 %, im anderen Fall sind sie gering.Next in Collect. Czechoslov. Chem. Comm. 25, 1324 (1960) and 29, 2264 (1964) describe synthetic processes in which carbazole is coupled in dioxane or in ethanol. The yields are 55% in one case and low in the other case.

Aus dem J.Org.Chem. 22, 562 (1957) ist ein Verfahren bekannt geworden, bei dem mit 1,4 % Ausbeute 4-Nitranilin auf N-Ethylcarbazol in Eisessig gekuppelt wird.From J.Org.Chem. 22, 562 (1957) a method has become known in which 4-nitraniline is coupled onto N-ethylcarbazole in glacial acetic acid in 1.4% yield.

Das Verfahren der schweizerischen Patentschrift 367 254 betrifft ein Verfahren zur Herstellung von in Wasser schwer löslichen Monoazofarbstoffen, bei dem nach Beispiel 1 die Kupplungskomponente in Eisessig gelöst wird. Wendet man dieses Verfahren auf die Herstellung des Farbstoffs der Formel I an, in der Hal Chlor und R Ethyl bedeutet, so erhält man eine Ausbeute von 80 %. Dieser Farbstoff ist, gefärbt auf Polyester, um ca. 50 % farbschwächer als der nach dem erfindungsgemäßen Verfahren hergestellte.The process of the Swiss patent specification 367 254 relates to a process for the preparation of water-poorly soluble monoazo dyes, in which, according to example 1, the coupling component is dissolved in glacial acetic acid. Applying this process to the preparation of the dye of the formula I, in which Hal is chlorine and R is ethyl, a yield of 80% is obtained. This dye, dyed on polyester, is about 50% weaker in color than that produced by the process according to the invention.

Nach Beispiel 1 der US-PS 3 787 178 wird die Diazokomponente zu einem Gemisch von Nitrosylschwefelsäure, Eisessig und Propionsäure gegeben. Dann wird eine Lösung von Butylcarbazol in Eisessig hinzugegeben. Wendet man dieses Verfahren auf die Herstellung des Farbstoffs der Formel I an, in der Hal Chlor und R Wasserstoff ist, dann wird ein schwärzliches Pulver erhalten, das den gewünschten Farbstoff nur zu ca. 46 Gew.% enthält.According to Example 1 of US Pat. No. 3,787,178, the diazo component is added to a mixture of nitrosylsulfuric acid, glacial acetic acid and propionic acid. Then a solution of butyl carbazole in glacial acetic acid is added. If this process is applied to the preparation of the dye of the formula I in which Hal is chlorine and R is hydrogen, a blackish powder is obtained which contains only about 46% by weight of the desired dye.

Es wurde nun überraschenderweise gefunden, daß man die Nachteile der bisherigen Herstellungsverfahren vermeiden und die Farbstoffe der Formel I in Ausbeuten bis über 99% herstellen kann. Das erfindungsgemäße Verfahren zur Herstellung der Farbstoffe der Formel I ist dadurch gekennzeichnet, daß das Amin der Formel II in 70 bis 100 gewichtsprozentiger Essigsäure bei 10 bis 35°C mit Nitrosylschwefelsäure diazotiert, der Essigsäuregehalt der Diazolösung durch Zugabe von Wasser auf 60 bis 85 Gew.% reduziert und bei 15 bis 45°C ein Carbazol der Formel III in fester Form oder in Form einer Suspension in 60 bis 100 gewichtsprozentiger Essigsäure eingetragen wird.It has now surprisingly been found that the disadvantages of the previous production processes can be avoided and the dyes of the formula I can be produced in yields of up to 99%. The process according to the invention for the preparation of the dyes of the formula I is characterized in that the amine of the formula II is diazotized in 70 to 100 percent by weight acetic acid at 10 to 35 ° C. with nitrosylsulfuric acid, the acetic acid content of the diazo solution by adding water to 60 to 85% by weight. % reduced and a carbazole of the formula III in solid form or in the form of a suspension in 60 to 100 percent by weight acetic acid is introduced at 15 to 45 ° C.

Als Amine der Formel II kommen 2-Chlor-4-nitranilin und 2-Brom-4-nitranilin in Betracht.Suitable amines of the formula II are 2-chloro-4-nitraniline and 2-bromo-4-nitraniline.

Der für R stehende Alkylrest sowie die als Substituenten für R in Betracht kommenden Alkoxy-, Alkoxycarbonyl- oder Alkoxyalkoxycarbonyl-Reste können geradkettig oder verzweigt sein. Beispiele für Carbazole der Formel III sind: Carbazol, ferner Carbazole, die am Stickstoff durch folgende Reste substituiert sind: Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, sek.-Butyl, 2-Hydroxyethyl, 4-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-n-Propoxyethyl, 2-i-Propoxyethyl, 2-n-Butoxyethyl, 2-i-Butoxyethyl, 3-Methoxybutyl, 4-Methoxybutyl, 2-Cyanethyl, 2-Methoxycarbonylethyl oder 2-Ethoxycarbonylethyl. Bevorzugte Reste für R sind Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Cyan-ethyl, insbesondere dann, wenn diese Reste zusammen mit Hal = Chlor in den Farbstoffen der Formel I auftreten. Das erfindungsgemäße Verfahren eignet sich ganz besonders zur Herstellung des Farbstoffs der Formel I mit Hal = Chlor und R = Wasserstoff.The alkyl radical representing R and the alkoxy, alkoxycarbonyl or alkoxyalkoxycarbonyl radicals which are suitable as substituents for R can be straight-chain or branched. Examples of carbazoles of the formula III are: carbazole, furthermore carbazoles which are substituted on the nitrogen by the following radicals: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, 2-hydroxyethyl , 4-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 2-i-propoxyethyl, 2-n-butoxyethyl, 2-i-butoxy ethyl, 3-methoxybutyl, 4-methoxybutyl, 2-cyanoethyl, 2-methoxycarbonylethyl or 2-ethoxycarbonylethyl. Preferred radicals for R are hydrogen, alkyl having 1 to 4 carbon atoms or cyanoethyl, in particular when these radicals occur together with Hal = chlorine in the dyes of the formula I. The process according to the invention is particularly suitable for the preparation of the dye of the formula I with Hal = chlorine and R = hydrogen.

Das Amin der Formel II wird in 70 bis 100 gewichtsprozentiger, vorzugsweise in 85 bis 95 gewichtsprozentiger, ganz besonders bevorzugt in 88 bis 92 gewichtsprozentiger Essigsäure bei Temperaturen von 10 bis 350C, vorzugsweise 10 bis 30oC, mit Nitrosylschwefelsäure, zweckmäßigerweise unter Rühren, diazotiert. Es ist zweckmäßig, wenn das Amin der Formel II vor bzw. während der Diazotierung in gelöster oder in fein verteilter Form in der Essigsäure vorliegt. Die erwünschte Feinverteilung wird z.B. dadurch erreicht, daß das Amin der Formel II in der Essigsäure vor der Zugabe der Nitrosylschwefelsäure unter Rühren bei Temperaturen von 15 bis 50°C, vorzugsweise 20 bis 40°C, möglichst vollständig gelöst wird und daß dann die Lösung auf die Diazotierungstemperatur abgekühlt wird, wodurch sich abscheidendes Amin in feiner Verteilung ausfällt.The amine of formula II is in 70 to 100 percent by weight, preferably in 85 to 95 percent by weight, very particularly preferably in 88 to 92 percent by weight acetic acid at temperatures of 10 to 35 ° C., preferably 10 to 30 ° C., with nitrosylsulfuric acid, advantageously with stirring , diazotized. It is expedient if the amine of the formula II is present in dissolved or finely divided form in the acetic acid before or during the diazotization. The desired fine distribution is achieved, for example, in that the amine of the formula II is dissolved as completely as possible in the acetic acid before the addition of the nitrosylsulfuric acid with stirring at from 15 to 50 ° C., preferably 20 to 40 ° C., and then the solution is dissolved the diazotization temperature is cooled, as a result of which the precipitating amine precipitates out in a fine distribution.

Die Diazotierung des Amins der Formel II mit Nitrosylschwefelsäure soll rasch, d.h. innerhalb von 5 bis 45, vorzugsweise innerhalb von 5 bis 20 Minuten erfolgen, da sich sonst das Triazen der Formel IV

Figure imgb0004
bilden würde, das in der eingesetzten Essigsäure sehr schwer löslich ist und daher ausfallen würde. Dies könnte zu örtlicher Überhitzung und damit zur Zersetzung noch vorhandener Diazoniumverbindung, zum Rührerstillstand und zum Abbruch der gewünschten Reaktion führen. Durch die rasche Zugabe der Nitrosylschwefelsäure wird das Milieu rasch so sauer, daß nur noch wenig freies Amin der Formel II vorliegt und die Triazenbildung weitgehend unterbunden bleibt. In geringem Maße entstandenes Triazen der Formel IV wird bei den beim erfindungsgemäßen Verfahren verwendeten Temperaturen zurückgespalten,und das dabei freiwerdende Amin der Formel II wird quantitativ weiterdiazotiert. Da die Zugabe der Nitrosylschwefelsäure exotherm verläuft und andererseits die Diazolösung nicht zu stark erwärmt werden darf, richtet sich die Zugabezeit für die Nitrosylschwefelsäure vor allem nach der Intensität, mit der während der Diazotierung gekühlt werden kann.The diazotization of the amine of the formula II with nitrosylsulfuric acid should take place rapidly, ie within 5 to 45, preferably within 5 to 20 minutes, since otherwise the triazene of the formula IV
Figure imgb0004
 would form, which is very sparingly soluble in the acetic acid used and would therefore fail. This could lead to local overheating and thus to the decomposition of the diazonium compound still present, to the stirrer stoppage and lead to termination of the desired reaction. The rapid addition of nitrosylsulfuric acid quickly makes the environment so acidic that only a little free amine of the formula II is present and the formation of triazene is largely prevented. Triazene of the formula IV formed to a small extent is split back at the temperatures used in the process according to the invention, and the amine of the formula II which is released in the process is quantitatively further diazotized. Since the addition of the nitrosylsulfuric acid is exothermic and, on the other hand, the diazo solution must not be heated too much, the addition time for the nitrosylsulfuric acid depends primarily on the intensity with which it is possible to cool during the diazotization.

Zweckmäßigerweise wird mit der Diazotierung knapp oberhalb der Temperatur begonnen, bei der die Lösung oder Suspension des Amins der Formel II fest wird, wobei es dann möglich ist, die Temperatur durch Eiskühlung unter 25 bis 350C zu halten. Nach der Zugabe der Nitrosylschwefelsäure wird noch einige Zeit zur Vervollständigung der Diazotierung nachgerührt und dann der Essigsäuregehalt der Diazolösung durch Zugabe von Wasser auf 60 bis 85 Gew.%, vorzugsweise auf 68 bis 73 Gew.%, reduziert. Der Essigsäuregehalt der Diazolösung darf durch die Zugabe des Wassers nicht unter 60 Gew.% fallen, da sich sonst die Kupplungskomponente nicht mehr ausreichend gut löst bzw. die Stabilität der Diazoniumverbindung abnimmt.The diazotization is expediently started just above the temperature at which the solution or suspension of the amine of the formula II becomes solid, it then being possible to keep the temperature below 25 to 35 ° C. by ice cooling. After the addition of the nitrosylsulfuric acid, stirring is continued for some time to complete the diazotization and then the acetic acid content of the diazo solution is reduced to 60 to 85% by weight, preferably to 68 to 73% by weight, by adding water. The addition of water should not drop the acetic acid content of the diazo solution below 60% by weight, since otherwise the coupling component will no longer dissolve sufficiently or the stability of the diazonium compound will decrease.

Um Nitrosierungsreaktionen an der Kupplungskomponente der Formel III zu verhindern, ist es vorteilhaft, den Überschuß des Diazotierungsmittels in der Diazolösung durch nitritzerstörende Mittel, wie Harnstoff oder Amidosulfonsäure, zu reduzieren oder zu beseitigen. Derartige Mittel können der Diazolösung vor oder nach der Verdünnung mit Wasser zugefügt werden.In order to prevent nitrosation reactions on the coupling component of the formula III, it is advantageous to reduce or eliminate the excess of the diazotizing agent in the diazo solution by means of nitrite-interfering agents such as urea or amidosulfonic acid. Such agents can be added to the diazo solution before or after dilution with water.

Die Kupplung wird bei Temperaturen von 15 bis 45°C, vorzugsweise 20 bis 35°C, durchgeführt, indem das Carbazol der Formel III langsam, z.B. im Verlauf von 1/2 bis 2 Stunden, zweckmäßigerweise unter Rühren in die Diazolösung eingetragen wird. Das Carbazol der Formel III soll dabei zweckmäßigerweise in feiner Verteilung vorliegen. Beim Eintragen eines Carbazols der Formel III in fester Form kann die Feinverteilung z.B. durch ein vorausgegangenes Mahlen des Carbazols zustande gekommen sein. Beim Eintragen des Carbazols der Formel III in Form einer Suspension in Essigsäure wird das Carbazol der Formel III zweckmäßigerweise zunächst in der fünf- bis fünfzigfachen Menge 60 bis 100 gewichtsprozentiger Essigsäure durch Erwärmen möglichst vollständig gelöst und dann auf eine-Temperatur, die nicht über der Kupplungstemperatur liegt, abgekühlt, wodurch das sich abscheidende Carbazol der Formel III in. feiner Verteilung ausfällt. Der Essigsäuregehalt des Kupplungsansatzes darf durch die Essigsäure der Suspension nicht unter 60 Gew.% gedrückt bzw. nicht über 85 Gew.% angehoben werden.The coupling is carried out at temperatures of 15 to 45 ° C, preferably 20 to 35 ° C, by the carbazole of formula III slowly, for example in the course of 1/2 to 2 hours, is expediently introduced into the diazo solution with stirring. The carbazole of the formula III should advantageously be in a fine distribution. When a carbazole of the formula III is introduced in solid form, the fine distribution may have been brought about, for example, by grinding the carbazole beforehand. When the carbazole of the formula III is introduced in the form of a suspension in acetic acid, the carbazole of the formula III is expediently first completely dissolved in 50 to 50 times the amount of 60 to 100 percent by weight acetic acid by heating and then to a temperature which does not exceed the coupling temperature is cooled, whereby the precipitated carbazole of the formula III precipitates in a fine distribution. The acetic acid content of the coupling batch must not be pressed below 60% by weight or raised above 85% by weight due to the acetic acid of the suspension.

Die Zugabezeit für dasCarbazol der Formel III richtet sich nach der Ansatzgröße und wird bei Ansätzen im kg-Maßstab zweckmäßigerweise auf 1 bis 2 Stunden ausgedehnt.The addition time for the carbazole of the formula III depends on the batch size and is expediently extended to 1 to 2 hours in batches on a kg scale.

Die Kupplungstemperatur darf 15°C nicht unterschreiten, da sich sonst das eingetragene Carbazol-Derivat zu schlecht löst und zu lange Kupplungszeiten erforderlich sind oder Farbstoffreingehalt und -ausbeute absinken, da der ausfallende Farbstoff Kupplungskomponente einschließt oder die Diazoniumverbindung sich bei zu langer Reaktionszeit zersetzt. Zweckmäßigerweise wird bei 20 bis 3C°C gekuppelt und die Reaktion bei Temperaturen bis 40°C zu Ende geführt.The coupling temperature must not fall below 15 ° C, otherwise the carbazole derivative entered will dissolve too poorly and coupling times will be too long, or the dye purity and yield will decrease, since the dye which precipitates includes the coupling component or the diazonium compound will decompose if the reaction time is too long. It is expedient to couple at 20 to 3 ° C. and to complete the reaction at temperatures up to 40 ° C.

Während der Kupplung fällt gebildeter Farbstoff aus, so daß fast die gesamte eingesetzte Essigsäuremenge als Lösungsmittel für die Diazoniumverbindung und die Kupplungskomponente zur Verfügung steht.Dye formed during the coupling precipitates, so that almost the entire amount of acetic acid used is available as a solvent for the diazonium compound and the coupling component.

Das erfindungsgemäße Verfahren liefert die Farbstoffe der Formel I in Ausbeuten von bis 99 % und mehr, in hervorragenden heinheiten. Die nohcren Reinheicen bewirken oei der coloristischen Anwendung höhere Farbstärken und zumeist auch bessere Werte für die Trockenhitzeplissier- und Trockenhitzefixierechtheit im Vergleich zu Farbstoffen, die nach anderen Verfahren hergestellt worden sind. Die bei dem erfindungsgemäßen Verfahren anfallende Essigsäurelösung kann wieder regeneriert werden.The process according to the invention provides the dyes of the formula I in yields of up to 99% and more, in excellent units. The low purities result in higher color strengths in the coloristic application and mostly also better values for the fastness to dry heat pleating and dry heat compared to dyes which have been produced by other processes. The acetic acid solution obtained in the process according to the invention can be regenerated again.

Beispielexample

In einem 6-1-Glaskolben werden 172,6 g (1 mol) 2-Chlor-4- nitranilin in 2506,0 g 90 gewichtsprozentiger Essigsäure bei 20 bis 40°C unter Rühren gelöst. Dann wird die Lösung auf 10° bis 15°C abgekühlt. Innerhalb 10 bis 15 Minuten läßt man nun unter Kühlung 326,0 g Nitrosylschwefelsäure zufließen. Dabei steigt die Temperatur im Kolben je nach Kühlintensität auf 20 bis 30oC. In diesem Temperaturbereich wird zur Vervollständigung der Diazotierung 30 Minuten nachgerührt. Dann wird die Diazolösung mit 680,0 g Wasser verdünnt und auf 30 bis 35°C erwärmt. Dann werden innerhalb von 30 Minuten bei 30 bis 35°C 175,5 g Carbazol eingetragen, und anschließend wird 2 Stunden bei dieser Temperatur gerührt. Zur Vervollständigung der Kupplung wird bei 35 bis 40°C nachgerührt. Nach 2 bis 3 Stunden ist die Kupplung beendet. Der Ansatz wird dann auf 10 bis 15°C abgekühlt, der Farbstoff abgesaugt und mit Wasser neutral gewaschen. Das Originalfiltrat und ein erster Teil des Wasserwaschfiltrats werden durch Rektifikation regeneriert.172.6 g (1 mol) of 2-chloro-4-nitraniline are dissolved in 2506.0 g of 90% strength by weight acetic acid at 20 to 40 ° C. in a 6-1 glass flask with stirring. Then the solution is cooled to 10 ° to 15 ° C. 326.0 g of nitrosylsulfuric acid are then allowed to flow in with cooling within 10 to 15 minutes. Depending on the cooling intensity, the temperature in the flask rises to 20 to 30 ° C. In this temperature range, the mixture is stirred for 30 minutes to complete the diazotization. Then the diazo solution is diluted with 680.0 g of water and heated to 30 to 35 ° C. Then 175.5 g of carbazole are introduced at 30 to 35 ° C. within 30 minutes, and the mixture is then stirred at this temperature for 2 hours. To complete the coupling, stirring is continued at 35 to 40 ° C. The coupling is complete after 2 to 3 hours. The mixture is then cooled to 10 to 15 ° C, the dye is suctioned off and washed neutral with water. The original filtrate and a first part of the water wash filtrate are regenerated by rectification.

Farbstoffausbeute: 345,5 g trocken, Reingehalt 99,6 %, entsprechend 98,6 % Ausbeute der Theorie; Schmelzpunkt 218 bis 224°C.Dye yield: 345.5 g dry, purity 99.6%, corresponding to 98.6% yield of theory; Melting point 218 to 224 ° C.

Nach dem erfindungsgemäßen Verfahren können die in der folgenden Tabelle aufgeführten Farbstoffe hergestellt werden:

Figure imgb0005
The dyes listed in the following table can be prepared by the process according to the invention:
Figure imgb0005

Claims (10)

1. Verfahren zur Herstellung von Azofarbstoffen der Formel 1
Figure imgb0006
in der Hal Brom oder Chlor und R gegebenenfalls durch Hydroxy, Cyan, Alkoxy mit 1 bis 4 C-Atomen, Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkoxyrest, Alkoxyalkoxycarbonyl mit jeweils 1 bis 4 C-Atomen in den beiden Alkoxyresten, substituiertes Alkyl mit 1 bis 4 C-Atomen oder Wasserstoff bedeutet, durch Diazotierung eines Amins der Formel II
Figure imgb0007
und Kupplung des diazotierten Amins auf ein Carbazol der Formel III
Figure imgb0008
und Isolieren des Farbstoffs der Formel I nach beendeter Kupplung, dadurch gekennzeichnet, daß das Amin der Formel II in 70 bis 100 gewichtsprozentiger Essigsäure bei 10 bis 35°C mit Nitrosylschwefelsäure diazotiert, der Essigsäuregehalt der Diazolösung durch Zugabe von Wasser auf 60 bis 85 Gew.% reduziert und bei 15 bis 45°C ein Carbazol der Formel III in fester Form oder in Form einer Suspension in 60 bis 100 gewichtsprozentiger Essigsäure eingetragen wird.1. Process for the preparation of azo dyes of the formula 1
Figure imgb0006
 in the hal bromine or chlorine and R optionally substituted by hydroxy, cyano, alkoxy with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, alkoxyalkoxycarbonyl with 1 to 4 carbon atoms in each of the two alkoxy radicals with 1 to 4 carbon atoms or hydrogen means by diazotization of an amine of the formula II
Figure imgb0007
 and coupling the diazotized amine to a carbazole of the formula III
Figure imgb0008
 and isolating the dye of the formula I after coupling is complete, characterized in that the amine of the formula II is diazotized in 70 to 100% by weight acetic acid at 10 to 35 ° C with nitrosylsulfuric acid, the acetic acid content of the diazo solution by adding water to 60 to 85% by weight. % reduced and a carbazole of the formula III in solid form or in the form of a suspension in 60 to 100 percent by weight acetic acid is introduced at 15 to 45 ° C. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein Carbazol der Formel III verwendet wird, bei dem R Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Cyanethyl bedeutet.2. The method according to claim 1, characterized in that a carbazole of the formula III is used, in which R is hydrogen, alkyl having 1 to 4 carbon atoms or cyanoethyl. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß ein Amin der Formel II mit HaI = Chlor und ein Carbazol der Formel III mit R = Wasserstoff verwendet wird.3. The method according to claim 1 or 2, characterized in that an amine of formula II with HaI = chlorine and a carbazole of formula III with R = hydrogen is used. 4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Amin der Formel II in 85 bis 95 gewichtsprozentiger, vorzugsweise 88 bis 92 %, Essigsäure diazotiert wird.4. The method according to one or more of claims 1 to 3, characterized in that the amine of formula II is diazotized in 85 to 95 percent by weight, preferably 88 to 92%, acetic acid. 5.Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Amin der Formel II innerhalb von 5 bis 45 Minuten, vorzugsweise innerhalb von 5 bis 20 Minuten, diazotiert wird.5.The method according to one or more of claims 1 to 4, characterized in that the amine of formula II is diazotized within 5 to 45 minutes, preferably within 5 to 20 minutes. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Essigsäuregehalt nach der Diazotierung durch Zugabe von Wasser auf 68 bis 73 Gew.% reduziert wird.6. The method according to one or more of claims 1 to 5, characterized in that the acetic acid content after the diazotization is reduced to 68 to 73% by weight by adding water. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Carbazol der Formel III bei 20 bis 350C eingetragen wird.7. The method according to one or more of claims 1 to 6, characterized in that the carbazole of formula III is entered at 20 to 35 0 C. 8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Carbazol der Formel III in feinverteilter, vorzugsweise feinverteilter, fester Form eingetragen wird.8. The method according to one or more of claims 1 to 7, characterized in that the carbazole of the formula III is introduced in finely divided, preferably finely divided, solid form. 9. Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Amin der Formel II vor der Diazotierung in feiner Verteilung vorliegt.9. The method according to one or more of claims 1 to 8, characterized in that the amine of formula II is present in fine distribution before the diazotization. 10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Carbazol der Formel III im Verlauf von 1/2 bis 2 Stunden eingetragen wird,10. The method according to one or more of claims 1 to 9, characterized in that the carbazole of the formula III is introduced in the course of 1/2 to 2 hours,
EP82109414A 1981-10-14 1982-10-12 Method of preparing azo dyestuffs by diazotation and coupling Expired EP0077066B1 (en)

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US4677386A (en) * 1985-07-31 1987-06-30 Chevron Research Company Method of interpreting impedance distribution of an earth formation obtained by a moving array using end emitting current electrodes sequentially activated and a series of potential electrodes
US4675610A (en) * 1985-07-31 1987-06-23 Chevron Research Company Method of logging an earth formation penetrated by a borehole to provide an improved estimate of impedance distribution with depth using a single continuously emitting current electrode and a multiplicity of potential electrodes of a moving logging array
US4675611A (en) * 1985-07-31 1987-06-23 Chevron Research Company Method of logging an earth formation penetrated by a borehole to provide an improved estimate of impedance distribution of the formation
US4714889A (en) * 1985-07-31 1987-12-22 Chevron Research Company Method of interpreting impedance distribution of an earth formation using precursor logging data provided by a multi-electrode logging array stationary within a borehole
US4703279A (en) * 1985-07-31 1987-10-27 Chevron Research Company Method of interpreting impedance distribution of an earth formation penetrated by a borehole using precursor data provided by a moving logging array having a single continuously emitting current electrode and a multiplicity of potential electrodes
PL169333B1 (en) * 1992-05-26 1996-07-31 Inst Chemii Przemyslowej Im Pr Reactive carbazole dyes and method of obtaining them
CN103497533A (en) * 2013-09-10 2014-01-08 江苏亚邦染料股份有限公司 Heterocyclic azo type disperse dyestuff and application thereof

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DE2338089A1 (en) * 1973-07-27 1975-02-06 Cassella Farbwerke Mainkur Ag Water-insol. mono-azo dyes free from ionogenic gps - used for dyeing synthetic hydrophobic materials

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US3897203A (en) * 1972-02-28 1975-07-29 American Color & Chem Carbazole dyestuffs

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